Study of the composition of the KCl – AlCl3 – ZrCl4 – HfCl4 melt in relation to extractive rectification of zirconium and hafnium chlorides

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In 2021, Chepetsk Mechanical Plant SC put into operation the production of a zirconium sponge of nuclear purity for the production of nuclear fuel components. The purification of zirconium from hafnium is carried out by extractive rectification in a KCl–AlCl3 melt. The experience of the plant operation has shown that the elemental analysis of the melt for the content of K, Al, Zr, Hf is not enough to determine its operational properties.

During the operation of the plant at various points of the technological scheme, the composition of the melt KCl–AlCl3–ZrCl4–HfCl4 was studied by a complex of independent methods using specially developed methods.

The content of the phases ZrCl4, K2ZrCl6 and AlCl3 against the background of the matrix phase KAlCl4 was studied in frozen melts by X-ray diffractometry. The regularities of changes in the content of ZrCl4, AlCl3 and K2ZrCl6 according to the technological scheme of the installation are established.

The content of the X-ray amorphous component, which contains up to 1.5 wt% aluminum and up to 3.5 wt% zirconium, has been established in frozen melts. By the method of reducing melting in the presence of carbon in frozen melts, the oxygen content of up to 1.8 wt% was determined, which is part of the X-ray amorphous component, presumably consisting of AlOCl and ZrOCl2.

A method for determining the AlCl3/KCl ratio based on the difference in the physicochemical properties of the melt components has been developed. Based on the results obtained, the melt composition was adjusted during the operation of the zirconium and hafnium chloride separation unit at ChMP JSC.

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作者简介

A. Panfilov

SC «TVEL»

编辑信件的主要联系方式.
Email: AVPanfilov@tvel.ru
俄罗斯联邦, Moscow

A. Korobkov

SC “Chepetsky Mechanical Plant”

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Glazov

V. Buzmakov

SC “Chepetsky Mechanical Plant”

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Glazov

V. Tereshinb

SC “Chepetsky Mechanical Plant”

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Glazov

A. Ivshina

Ural Federal University named after the First President of Russia B.N. Yeltsin

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Yekaterinburg

A. Abramov

Ural Federal University named after the First President of Russia B.N. Yeltsin

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Yekaterinburg

D. Danilov

Ural Federal University named after the First President of Russia B.N. Yeltsin

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Yekaterinburg

A. Chukin

Ural Federal University named after the First President of Russia B.N. Yeltsin

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Yekaterinburg

I. Polovov

Ural Federal University named after the First President of Russia B.N. Yeltsin

Email: AVPanfilov@tvel.ru
俄罗斯联邦, Yekaterinburg

参考

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  5. Delpech S. Molten salts for nuclear applications. – In: Molten Salts Chemistry. From Lab to Applications / Ed.F. Lantelme, H. Groult. / Amsterdam. Boston. Heidelberg et al.: Elsevier. 2013. 24. P. 497–520.
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  10. Nekhamkin L.G. Metallurgiya cirkoniya i gafniya [Metallurgy of zirconium and hafnium]. M.: Metallurgiya. 1979. 208 p. [In Russian].
  11. Panfilov A.V., Korobkov A.V., Buzmakov V.V., Tereshin V.V. Izuchenie processa desorbcii tetrahlorida cirkoniya iz rasplava KCl–AlCl3 [Study of the desorption of zirconium tetrachloride from the KCl – AlCl3 melt] // Voprosy atomnoj nauki i tekhniki. Seriya: Materialovedenie i novye materialy. 2022. 115. № 4. P. 58–65. [In Russian].
  12. Ivshina A.A., Abramov A.V., Chukin A.V., Polovov I.B., Danilov D.A., Denisova O.V. and Karpov V.V. // AIP Conference Proceedings. 2022. https://doi.org/10.1063/5.0088853
  13. Karpov V.V., Polovov I.B., Kudryashova D.V., Lisienko D.G., Volkovich V.A., Chukin A.V. and Rebrin O.I. Indirect methods of determination of K: Al mole ratio in molten chloroaluminates // The Electrochemical Society. 2014. 64. № 4. P. 461–472.
  14. Kartashova E.S., Danilov D.A., Polovov I.B. // AIP Conf. Proc. 2022. 2466. № 1. Р. 050016.https://doi.org/10.1063/5.0088865.
  15. Dulepov Yu.N., Zvonkov I.N., Skiba K.V., Chinejkin S.V., Shipulin S.A., Krickij A.A., Panfilov A.V., Karimov I.A., Korobkov A.V. Sposob povysheniya effektivnosti rektifikacionnogo razdeleniya tetrahloridov cirkoniya i gafniya [A method for increasing the efficiency of rectification separation of zirconium and hafnium tetrachlorides]. Pat. RU2745521. 2020. [In Russian].

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2. Fig. 1. Dynamics of changes in the molar ratio of Al/K in the KCl–AlCl3–ZrCl4–HfCl4 melt of the zirconium and hafnium chloride separation plant of CHMP JSC during operation.

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3. Fig. 2. Schematic diagram of the installation for determining the residual zirconium content in the melt

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4. Fig. 3. Schematic diagram of the installation: 1 – unit for preparing a separable mixture of zirconium and hafnium chlorides; 2 – distillation column; 3 – evaporator; 4 – desorption column; sampling points: UP-1 – after dissolving the separable mixture of ZrCl4 and HfCl4 in the KCl – AlCl3 melt; UP -2 – after the distillation column; UP-3 – after the boiler of the distillation column; UP-4 – after desorption of ZrCl4 by an inert gas stream.

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5. Fig. 4. Typical diffractograms of frozen melts: a – the presence of phases KAlCl4 and ZrCl4; b – the presence of phases KAlCl4, ZrCl4 and AlCl3; c – the presence of phases KAlCl4 and K2ZrCl6.

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6. Fig. 5. Correlation between the Zr content in the crystalline phases of ZrCl4 and K2ZrCl6 and the Zr content determined by inductively coupled plasma atomic emission spectrometry.

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7. Fig. 6. Correlation between the Zr determined by the spectrometric method in UP-4 and the Zr content in the K2ZrCl6 phase.

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